JPS60151001A - Protective liquid for wood - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION As it is desired to protect wood from decay caused by microorganisms, several compounds with antimicrobial properties have been proposed as useful wood-preservers.
ing) agent.

Wood can be used, for example, in wood products such as lumber, sawn timber, railway sleepers, telephone poles, fences, wood cladding, wickerwork, plywood, hardboard, wafer board, clipboard, sillage, etc. Considered as a wood product commonly used in the construction of bridges or houses.

Wood that is protected from decay and rot is susceptible to mold, blight, loss of its useful mechanical properties such as breaking strength, resistance to impact and shear strength, or loss of its optical or other properties. Useful properties such as reduced odor production, protection from microbial decay, gvot (gvot) formation and dots (As)
pergtllug) species, Penicillium (16% 1c
tlliurn) species, Aureobasidium pallu-lαna
), Sclerophoma biteophylla (Sclerop)
homa pityophila), Mold (Ver.
ttotlliiw'm) species, incomplete fungus (Alter)
narta) species, Rhi-zopws
) species, Mwcor species, Pecilomyces (
paectlomycea)@, Yeast (Saoc)
haromyces) species, Trichoderma viride (T.
rtchoderma virtdg), Chaetomium globo-a
urn), Stachybotrys atla (Stachy-b
otrys atra), Myrothecium verrucaria,
Oospora lacte, x, (Oospora 1act
) and other decay and wood-rotting fungi (frbng
ws). Molds and disintegrating tubes such as Aspergillus black mold (A
pencillium fwntc
ulosum), trichodel? - Viride (Trtcho)
dgrma v ride), Alternaria altermat
a) rot and goftrot fungi such as Chaetomium globosum;
boaum), Trycophyton
悌ENTAGROHY-TEA),・Coriolus・
Verge color (Cor I〇-1ug veraicol)
or ), Funiophora cerevera (Contopho
ra cerebe lla), Poria monttcola, and MarrL-1ius.
(Serpwla) lacrymans) and Lenzittta trabea
), as well as yeasts such as Candida
dαalbtcans) and yeast (Saccha
romy-ces) species should be emphasized.

In order to protect the wood from decay, it is treated with a composition containing one or more wood protectants. Such treatments can be carried out in several different ways, e.g. by treating the wood in closed pressure or vacuum systems, in heat or dipping (did) systems, or by extensive external wood structural treatments, e.g. Brushing (brwsh-ing), dipping (ct, tp) the wood with a composition containing a wood protectant.
It is applied by spraying, spraying or soaking.

Although non-organic compounds have been used as wood protectants, more recent preferred reagents are organic compounds, such as the azoles described in EP 38.109. Due to their organic nature, these compounds are somewhat lipophilic and dissolve well in organic media, but often give inadequate solubility in aqueous media. Therefore, these organic reagents are usually incorporated into organic compositions for application to wood.

However, these compositions have certain drawbacks, such as the expense associated with adverse effects on the environment and the safety and health of the users. Accordingly, a number of organic liquids have recently been developed that form emulsions or dispersions with aqueous media, such as those described in US Pat. No. 4,357,163. however,
These emulsions or dispersions that result after mixing an organic liquid with an aqueous medium are too dependent on many factors, such as changes in temperature, pH value of the mixture and/or hardness of the water used, and therefore the presence of impurities in wood etc. This often results in inadequate physical stability.

In addition, in order to establish a continuous process in a closed pressure or vacuum system or in a thermal or immersion technique, it is necessary that the concentration of the active agent does not change much in the composition, so that the suspension Alternatively, non-uniform uptake of the dispersion adversely affects the use of the suspension or dispersion in such technology. Such lack of uniform uptake causes a decrease or increase in the concentration of active agent in the remaining composition, ultimately resulting in dilution of the composition and precipitation of the wood protectant, respectively.

The present invention m) formula %formula% 1 CB, -R.

In the formula,
CH, -CM, -CM, -1-CB (C1l,) -c
H(CHs)- or -CE, -CE(alkyl)-, where the alkyl is a linear or branched C1-
"1G is an alkyl group, +KAr is a halogen, 01
~C6 alkyl group, CI~C6-alkoxy group, cyano-, trifluoromethyl- or moyo-phenyl group substituted with 1 to 3 nitro groups, chenyl-, halothenyl-, naphthalenyl-mata is a fluorenyl group; and said R is C1-CIo alkyl, cycloalkyl, cycloalkyl-lower alkyl, lower alkenyl, aryl-lower alkyl, aryloxy-lower alkyl, or a group of formula -〇-R0, where said RoiiCI-C
*o alkyl, lower 7 is kenyl, lower alkynyl or aryl lower alkyl, where the aryl group is phenyl, naphthalenyl or substituted phenyl, where the substituted phenyl is halo, cyano, nitro, phenyl , lower alkyl and lower alkoxy, provided that if more than one substituent is present, only one of them may be cyano, nitro or phenyl. The present invention relates to a mainly organic wood protection liquid dilutable in an aqueous medium, containing from 0.01% to 10% by weight of at least one azole or its acid addition salt having the following properties.

The wood protection liquids have the advantage that a homogeneous aqueous solution is produced almost instantaneously by mixing these liquids with a predominantly aqueous medium. Furthermore, these solutions have extremely high physical stability not only at ambient temperatures, ie temperatures comprised between 15°C and 35°C, but also at low temperatures. This aqueous solution is
Even after several crystallizations at °C and subsequent storage at ambient temperature, the physical stability is not adversely affected.

This homogeneous solution also has good wetting properties on the wood surface due to the high temperature penetration of the solution into the wood, which results in an unexpectedly high uptake of the solution by the wood, resulting in better treatment. The wood that will be covered will be well protected.

In addition, due to the homogeneous uptake of the aqueous solution, the wood protection liquid and the resulting aqueous solution are particularly useful for treatment techniques requiring continuous process possibilities, such as impregnation or dipping techniques.

In addition to the above-mentioned advantages, the present composition, when used in aqueous solution, provides
It also has the advantage of protecting treated wood to the same extent with a lower amount of active ingredient incorporated into the wood than when using solvent-based mixtures.

In addition to the above-mentioned advantages, the solutions produced using wood protection fluids have, in addition, advantages mainly characteristic of aqueous media, such as a relatively high flash point <flα5h-p6int), 3
! ! It has a combination of low toxicity, lack of irritation, etc. which has a favorable impact on the environment and health as well as the safety of the user.

Of particular interest are liquids according to the invention having the formula % ■ CM, -R,' where X has the meaning given above and R1' is a radical of the formula, where Z' is a radical - CD, -CH, -1-C
H, -CB, -CH, -1-CH(CH,)-CH, -
1-C1l (C, HIl) -C1lt-1, -CE
(C,R7)-CM,-1-CH(CH,)-Cl
l (CE,)- or -CH(CH&)-CH(Cx
Hs)-, and IAt" is an unsubstituted phenyl or atom, preferably a phenyl substituted with a chlorine atom, a CI-C6 alkyl group, a C1-C6 alkoxy group, a cyano or nitro group, and ;
and R' is 01-C6 alkyl or C8-C4 alkenyloxy.

Of further particular interest are liquids according to the invention of the formula %, in which X has the meaning given above and RI' is a radical of the formula, where R" is C8-c4 alkyl, CI"
C4 is lower alkenyloxy, R3 is hydrogen or C1-C, alkyl, and n is 1 or 2.

A preferred liquid according to the invention is 1-[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-ylmethyl]-IB-1.2.4-triazole, generally associated with azaconazole. or appropriate acid addition salts thereof.

Since the wood protection solution mainly needs to form a homogeneous solution with the aqueous medium, the solubilizer must sufficiently solubilize the active agent and the solvent of the liquid in the aqueous medium, and the The solubility of the active agent must not be adversely affected.

addition product with 1 mole of phenol containing a suitable solubilizer; and II)
Addition products of 1 to 60 moles of ethylene oxide with 1 mole of ricinus oil.

The most preferred solubilizers are 1) addition products of 1 to 60 moles of ethylene oxide with 1 mole of nonylphenol or octylphenol/I/1; and 11) addition products of 1 to 60 moles of ethylene oxide with 1 mole of cinnamon oil. , select from the group consisting of.

This liquid organic solvent must fulfill the requirement of sufficiently dissolving the active ingredient and, together with the solubilizing agent, being homogeneously miscible with the predominantly aqueous medium. 'Suitable solvents are 2-butoxycetanol and butyl-2-hydroxyacetate.

In the compositions of the invention, the azole of formula (1) may also be used as a btoctdal compound such as an antimicrobial agent.
It can be used in combination with other compounds having useful activities such as microbial agents, insecticides, etc.

The following groups of products can be considered as antimicrobial agents which can be used in combination with the azoles of formula (1): phenol derivatives such as 3,5-dichlorophenol, 2,5-dichlorophenol, 3,5-dibromophenol , 2,5-dibromophenol, 215-(or 3.5)-dichloro-
4-bromophenol, 3,4,5-trichlorophenol, chlorinated hydrodiphenyl ethers e.g.
-Hydroxy-3,2',4'-) dichlorodiphenyl ether, phenylphenol, 4-10-2-phenylphenol, 4-chloro-2-benzylphenol, dichlorophene, hexachlorophene: aldehyde examples: evaformaldehyde, glutaraldehyde, salicylaldehyde alcohol such as phenoxyethanol;
Antimicrobially active carboxylic acids and their derivatives; organometallic compounds such as tributyltin compounds; iodine compounds such as iodophors, iodonium compounds; mono-, di- and polyamines such as dodecylamine muffs 1.1
0-di(n-heptyl)-1,10-diaminodecane;
Quaternary ammonium compounds such as benzyl-dimethyldodecylammonium chloride, dimethyldodecylammonium chloride, penzyl-di(2-hydroxyethyl)dodecylammonium chloride; sulfonium- and phosphonium compounds; mercapto compounds and their alkaline earth and heavy metal salts such as 2- Mercaptopyridine-■-oxide and its sodium and zinc salts, 3-mercaptopyridazine-2-oxide, 2
-Mercaptoquinoxaline-1-oxide, 2-mercaptoquinoxaline-di-oxide, as well as symmetrical disulfides of nuclear mercapto compounds 1-urea such as tripromo or trichlorocarboanilide, dichloro-trifluoromethyl-diphenylurea: tribromosalicylte□ Nilide; 2-bromo-2-nitro-1,3-dihydroxypropane; dichlorobenzoxacilone; chlorhexidine; isothea- and penzizothiazolone derivatives.

The following groups of products can be considered as pesticides which can be used together with the azoles of formula (I): pesticides with natural products such as nicotine, rotinone, biletrum, etc. monochlorinated hydrocarbons such as lindane, chlordane, endosulfan compounds such as diazinon, parathion, dichloroorbos, dimethoate, etc.; carbamates such as carboaryl, aldicarbo, meteocarbo, globoxur, etc.; biological insecticides such as Bacillus thuringiensis
enaia); synthetic birethroids such as permethrin, allethrin, cibamethrin, halotrin, etc.

Furthermore, the composition of the invention may also contain additives that can improve its adaptability, chemical and/or physical stability and similar properties of the core composition. Examples of such additives include natural and synthetic resins such as wood resins, acacia resins, polyurethane resins, drying oils such as linseed oil, otticica oil, fish oil, stand oil, etc., desiccants such as e.g. There are naphthenoates, stabilizing products such as UV pulling agents, antioxidants, pigments, and waxes with high softening points.

Experimental Section The following examples are illustrative of the invention and are not intended to limit the scope of the invention. All parts herein are parts by weight unless otherwise specified.

In the following examples, Cem, also MP 8■i
d/ is a trademark for the mixture of addition products of nylphenol with ethylene oxide, in which an average of 8 moles of ethylene oxide is reacted with 1 mole of nonylphenol, and Sopγoph, or B■ is the mixture of addition products of ricinus oil with ethylene oxide. is a trademark of a mixture of Octylphenol 8.5 is a mixture of addition products of octylphenol and ethylene oxide, in which an average of 85 moles of ethylene oxide was reacted with 1 mole of octylphenol.

A. Preparation of Organic Concentrates: Example 1 Composition 1: Azaconazole 3.3% by weight Lindane 1.8
Weight % 2-butoxyshetanol 50Xik%; and Cem1aol NP 8■ plus 100%.

Preparation 33 parts of nazole and 1.8 parts of lindane were added in portions to 50 parts of 2-butoxyethanol at 50°C. After complete dissolution, the mixture was cooled to 25° C. and 8449 parts of Cemulsol HP were added.

Example 2 Following the preparation method described in Example 1, the following compositions were prepared: Composition 2; 5% by weight of azaconazole; 50% by weight of 2-butoxethanol; and Cemulaol? iP 8■ plus 100%.

Composition 3: Added 1.83ii% azaconazole, 3% by weight lindane and butyl 2-hydroxyacetate, and gave 100 mA'.

Composition 4: azaconazole 5.0 wt% permethrin 1
0% by weight -29-butyl 2-hydroxyacetate 20% by weight; and 638% by weight of 5oprophor B.

Composition 5: 5.0% by weight of azaconazole, 10% by weight of carbosulfan, 20% by weight of butyl 2-hydroxyacetate and 8% by weight of Cgmwlsol MP.

Composition 6: Azaconazole 5.0% by weight 5opropl
Lor B■ 56% by weight rich butyl 2-hydroxyacetic acid plus 100-0 Composition 7: azaconazole 5.7% by weight butyl 2-hydroxyacetic acid ester 480% by weight; 5oprophor B■ 44.3% by weight di- and colophonium resin 2 weight%.

Composition 8: 5.7% by weight azaconazole, 48.0% by weight butyl 2-hydroxyacetate; 44.3% by weight 1 and 2% by weight petroleum resin.

Composition 9: 5.7% by weight azaconazole, 48.0% by weight butyl 2-hydroxyacetate, 44.3% by weight stem 5oprophor B; and 2% by weight alkyd resin 50F.

Composition 10: 5.7% by weight of azaconazole, 45.0% by weight of butyl 2-hydroxyacetate, 44.3% by weight of Oprophor B; and 5.0% by weight of alkyd resin 50F.

Composition 11: 5.7% by weight of azaconazole, 40.0% by weight of butyl 2-hydroxyacetate, 44.3% by weight of 5oprophor B8 and 10.0% by weight of alkyd resin 150F.

Composition 12; azaconazole 5.0] ii% acetic acid 1.2
% by weight i Butyl 2-hydroxyacetate 40.0% by weight Soprophor B 44.3% by weight i and alkyd resin 50F 8.8% by weight.

Composition 13: Etaconazole (1-[2-(214-dichlorophenyl)-4-dityldioxo-2-2-yl]methyl)-1#-1,2,4-triazole) 5% by weight Butoxetanol 50 Composition 14: Etaconazole 10% by weight Octylphenyl 8.5 203iJi%; Acetic acid 2% by weight: polysolvan 0010% by weight; and Cttmulaol MP 8% by weight.

Composition 15; Etaconazole 5% by weight 5oprpphor B■ 56% by weight; and polysolvan 0039% by weight.

Composition 16: Propiconazole (1-(C2-(2,4
-dichlorophenyl)-4-propyl-1,3-dioxo2-2-yl]methyl)-i, Z7-x.

2.4-triazole) 5.0% by weight Butyl 2-hydroxyacetate 40.7% weight 5oprophor　B■443wt%1 and Alkyd resin 50F 10% by weight.

Physical stability of the B0 composition: Example 3 1100 parts of the composition were stored at 20°C for 24 hours and subsequently at -7.5°C for 24 hours. The storage cycle is 14
I kept going back and forth for days.

Some compositions crystallized during storage at -7,5°C, but 2
The mixture always became completely homogeneous without any crystals precipitating during storage at 0°C.

Example 4 Compositions 2-16 were also prepared at 20° C. according to the method described in Example 3.
and stored at -7.5°C for 14 days.

The mixture became completely homogeneous during storage at 20° C. without any crystals precipitating.

Example 5 Compositions 1-16 in distilled water at 100-10,000 ppr
The prepared aqueous solution was incubated at 20 °C for 24 h by diluting to a final concentration of active ingredient of n and subsequently at -7,5
Stored at ℃ for 24 hours. This storage cycle was repeated for 14 days.

Most of the aqueous solutions crystallized or became heterogeneous during storage at -7.5°C, but were homogeneous or easily became homogeneous during storage at 20°C.

C9 Wood Uptake Example 6 A block of beech wood measuring 2 cm x 2 crn x 2 α was stored for a predetermined time in a desiccator containing a saturated solution of sodium dichromate at room temperature with a confirmed relative humidity of 52%.

The active ingredient composition organic solvent type protectant is white spirit (whi
te spirit), for plasticization (plastt-f
ytinty) solution consisting of a co-solvent and a resin contained 10F azaconazole per 11 parts. Water-based (Wαt
erbornt) type protectants were prepared as described above.

Radiolabeled active ingredients, especially azaconazole labeled with 14C on the 2-ethyl carbon, are 2. ．． It showed a specific activity of 22 μCi/η. distilled water 25
140 of 2.511 II per 4 - Azaconazole or White Spirit 20 Go Yuri 1.25 ■ 14 (:'
- A stock solution containing azaconazole was prepared.

An equal treatment solution of p3I azaconazole per treatment solution 11 was chosen to compare each type of protectant, so the active ingredient composition was diluted with an appropriate solvent. At the same time, a radiolabeled active ingredient was spiked to facilitate analytical procedures.

The composition of the treatment solution containing azaconazole is shown in Table 1.

A blank processing solution was prepared from the blank composition using the same dilution ratio.

Composition of oil paste-I and oil base-I liquid; azaconazole 10 g colophonium resin 50 g dibutyl phthalate 50 y polysolvan O 100 d white spirit plus 1000 m/white spirit plus 1000 m Method A, soaking treatment Humidity-controlled wood blocks were pre-treated. Weighed and placed individually into labeled 5-capacity glass beakers,
The weight was then recorded. To evaluate the moisture content at 52% relative humidity, 5 blocks were incubated at 120 °C for 2
It was dried for 4 hours. Three cubes were given for each protectant type hour combination; one cube was included as a blank treatment for each protectant type hour combination. Take out this block in a beaker,
Meanwhile, 15 rne of the selected treatment solution was added to each beaker. The initial weight of the treatment solution was recorded. The block was immersed in the solution and held to ensure complete immersion by the tip of a Pasteur pipette supported in a rack-mounted clamp. The beaker containing the organic solvent type protectant was coated with Paraftlm to reduce evaporative losses. After the predetermined contact time, ie 1 hour, 4 hours or 24 hours, the block was removed from the solution and secured in a clamp for leakage. The process was considered complete after 15-30 minutes. The final weight of the treatment solution was determined. After air drying for 2 hours, place the treated blocks into pre-weighed and labeled beakers and store at 52
Transferred to a %RE dessicator. The desiccator was evacuated periodically to remove volatile solvents.

Sample analysis The radioactivity of the treatment solution was measured by liquid scintillation counting (LSC) before and after immersion in the treatment solution.

Add 1 solution of In5ta-Gel I (Packard
)Scintillator cocktail (cockttttl)1
0- was completely mixed. Automatically quench (-quenc
h) and pac to correct luminescence and convert cpm (counts per minute) to dpm (disintegrations per minute).
A kard Tri-Carb 4530 microprocessor-controlled liquid scintillation spectrometer was used.

Two consecutive bands of five wood blocks were marked on the surface of the blocks in a direction parallel to the wood fibers. Pente this block.
It was fixed in a bench-vice and the bands between each two were scraped off. Shavings were collected on a plastic sheet fixed on a vent pipe. Combust corn
a ombws t.

-cones) (Packard),
Soshiz, packard 306B Sample 0
Burned in a ztdezer. The generated l'CO2 is converted into C
arbo-5orb-packard (7ml)
) and use the apparatus described above to trap perm
αf11LorV (Packard) (12rn
Radioactivity counting was performed in t).

CalculationThe amount of active ingredient transferred from the treatment solution to the wood is calculated using the formula % starting from the radioactivity balance, where F7 is the initial treatment solution weight η) and Ff is the amount of treatment solution after immersion. and d p m 4
and d p trLl is the amount of radioactivity (dpm/g) in these operating steps, and y is the specific volume of the treatment solution (i/1
1), and d p tn t is the total amount of radioactivity transferred from the solution during soaking. The radioactivity amount (dpm/at) of the initial treatment solution and its active ingredient concentration, ct (μ
Using the relationship between m17m1), the total active ingredient transfer was obtained from Eq. In this case, the unit weight of dry wood) F8 equivalent, FA (g) represents the loading of the active ingredient of this wood, and the formulas fl) and (2) are combined: X / F6 = (F < d 9 rn 4-Wl
°d9 trLf) (3) B. Impregnation treatment Dried wood specimens were divided into 5 sets of 15 pine wood blocks and 5 sets of 15 beech wood blocks, one set corresponding to each composition type. . A predetermined group is collected in a beaker and bαitαsting
weight and placed in a vacuum dessicator. Le
The pressure was reduced to 10mm Hg using a ybold-Herα-eus SEA vacuum pump. After 15 minutes, the prescribed treatment solution was introduced into the desiccator through the tube leading to the beaker.

Excess foaming was removed. The vacuum was released when the block was coated. The beaker was removed from the desiccator and left for 2 hours to complete impregnation. The block was then lifted from the treatment solution, allowed to drip for 1 minute, and weighed (weight knee after treatment). The block was air dried for 5 hours at room temperature in a forced exhaust fume hood.

Five blocks were randomly taken for analysis and stored in the dark at 25°C to ensure residual block stability; +5 blocks for 2 weeks and 5 blocks for 7 weeks.

The procedures outlined for each of the ten wood-composition type combinations were followed.

Measurement of active ingredients Immediately after processing the wood specimens, the concentration of active ingredients in the wood blocks was measured by radiometry. The block was secured in a pliers vise and the symmetrical halves were removed. The shavings were collected on a plastic sheet and made very homogeneous. Combine the four 50■ parts with Combusto-Co.
Weigh into an iLas (packard), and
ackard 306 BSample 0zidts
It burned in the er. The generated r4CQ is
-5orb It (packard) (7-) and permafluor v (pack
ard) (12 ml) as described above. Additionally, wood shavings were mixed with dichloromethane for blocks treated with oil-based compositions and methanol for blocks treated with water-dilutable compositions at 2o:x(v:W). Solvent extraction was carried out at a solvent:solid ratio. Four consecutive extractions were performed over 24 hours. The extracts were combined, adjusted to a known volume, and added as a scintillation cocktail directly to the solvent evaporation residue of 1 ml of methanol extract or dichloromethane extract 1- with In5ta-Gel 11 (pa, ckard) as described above. Radiometric analysis was performed as follows.

Calculated concentration of azaconazole in wood, Lw(gα, i/
m wood) was obtained as follows: where U is the treatment solution uptake (I number for one test block) and CO is α, i in the treatment solution.

is the concentration (11 grams in grams), do is the density of this solution (11!9 in grams), and Wo is the weight (F) of the test block. Also, the azaconazole loading can be expressed on a volumetric basis (i.e. α, i, /go wood): where r is the volume of the wood block (6 cd)
.

The concentration was obtained by measuring the amount of radioactivity.

D. Efficacy Example 7 1. Experimental method ■, 1. Substance α) Test bacteria: Coriolus versicolor (Cortolwsvers)
Tcolor) 863 A or Coniophora puteana were grown on malt agar at 25° C. in Pe) IJ dishes with a diameter of 120 mm. In this test, cells cultured for 20 days were used.

b) Test wood; Wood blocks (5 x 2 x 0.6 c
rIL) (beech wood or pine wood) was used.

C) Test solutions: Test solutions were prepared by dissolving the desired amount of the relevant composition in distilled water or xylene.

■、2. Method α) Treatment in protection of wood blocks The test blocks were dried in an oven at 100-110° C. for 18 hours, cooled in a desiccator and weighed (i.e. initial dry weight). The test block was weighed into the bottom of a Petri dish and placed into a vacuum dessicator. Reduce the pressure to 40 mbar using a water pump and pass the protective solution or blanco into the block through the tube leading to the bird dish.
ao) solution was impregnated. When the block is well covered, release the vacuum and remove the Petri dish from the desiccator.
The block was then left for 4 hours to saturate and sterilize. A control block was treated with a similar sterilization method by impregnating the wood block with Blanco solution. The blocks were filled with sterile filter paper and weighed under sterile conditions (
i.e. weight after treatment).

The amount of protectant taken up by the block was calculated (ie protectant in the wood).

b) Inoculation of blocks After drying for 6 days in a box with laminar air flow, the blocks were transferred to inoculation Petri dishes and inoculated into two blocks, one treated with protectant and one control block. Coriolus nokuichi color (CortoLu
a veraiaolor) or Coniophora butiana (Coniophor αput-αnα). A pair of blocks were selected in the same weight range.

C) Test period The test blocks were exposed to fungal challenge for 8 weeks at 25°C.

Petri dishes were placed together in a plastic bag to avoid drying.

d) Experimentation of the test block after exposure to fungal attack The mycelium adhering to this block was removed, dried in an oven at 100-110°C for 18 hours, cooled in a desiccator and weighed (i.e. the final dry weight).

2. Results Table 7 represents the toxicity thresholds for aqueous and oil-based mixtures. The toxicity threshold used herein is 3% by weight.
Wood that protects wood from decay in such an amount that the loss of
The amount of azole per m.

The percentage of weight loss was found to follow the formula %, and the amount of test compound adsorbed per x m of wood was found to follow the formula %, which gives the meaning of the concentration of the protectant in the test solution and the density of the test solution. have

Because it is impractical to define the exact amount of azole/go wood that will protect the wood from rotting in an amount that results in a loss of exactly 3% by weight, Table 7 shows the range in which the exact amount is included. It represents. The range is a low amount, i.e. 3% by weight
It is limited by the highest tested amount that results in a loss as large as υ, and the lowest amount that results in a high amount, ie, a loss as small as 3% by weight.

Continued from page 1 Inventor Thio France Mali Cornelius Lili Belgium 169 Inventor Leo Jan Josef Hijuan Reenbut Belgium 18- -- 2151- Frimelen Ant Belpusebe'---
3118-Bachelzer-Hercht Shinj Sdraef 16

Claims (1)

[Claims] 1.1) Suitable solvent 10% to 80% by weight, if)
20% to 80% by weight of a suitable solubilizer, and 111) Formula% Formula% where X is nitrogen or a CE group and R is a group of formula, where Z is a group -CH, -CM! -1-CM
, -CM, -CE, -1-CE (CH,)-CM
(CD,)- or -〇M, -CM(alkyl)-, where the alkyl is a straight or branched CI-
CIo alkyl group; Ar is optionally halogen, C1
~co alkyl group, C8-C0-alkoxy group, cyano-, trifluoromethyl- or nitro group substituted with 1 to 3 groups and is a moyo-phenyl group, chenyl-, halothenyl-, naphthalenyl- or tahafluorenyl group, and R is C1-CIo alkyl, cycloalkyl, cycloalkyl lower furkyl, lower alkenyl, aryl lower alkyl, aryloxy lower alkyl or a group of formula -0-Ro, where said Ro is C1-CIo
alkyl, lower alkenyl, lower alkynyl or aryl lower alkoxy, where the aryl group is phenyl, naphthalenyl or substituted phenyl, where the substituted phenyl is halo, acyano, nitro,
having 1 to 3 substituents selected from the group consisting of phenyl, lower alkyl and lower alkoxy, provided that if more than one substituent is present, only one of them is cyan, nitro or phenyl; A water-dilutable wood protection liquid comprising from 0.01% to 10% by weight of at least one azole or its acid addition salt having the following properties. 2 an azole with the formula % formula % where XFi7v or CM and R1' is a group of formula where Z' is a group -CH, -CH, -1-C
B! -CH, -CM, -1-C1l (CB,)-CM
, -1-CH(C2B,)-C1l, -1-CH(
C,H,)-C1l,-1-CB (CM,)-CM
(CB,)- or -CH(CHIl)-CM (C,
R6)-: Ar' is an unsubstituted phenyl or halogen atom, preferably a chlorine atom, a Cl-06 alkyl group, C. - phenylteacyl substituted with 1 to 3 C6 alkoxy groups, cyano or nitro groups; and R' is C8-C6
The liquid according to claim 1, selected from compounds having: alkyl or C8-C4 alkenyloxy. 3, azole with the formula % formula % where X is ■ or CH, and 1' is a group of the formula, where R" is C1-C4 alkyl, C1-
C4 lower alkenyloxy, R3 is hydrogen or C
8-C, alkyl, and n is 1 or 2. The liquid according to claim 1, selected from S compounds having the following. 4. Azole is 1-(:2-(2,4-dichloro7ethyl)-1,3-')oxolan-2-ylmethyl)
The liquid according to claim 1, which is -1M-1,2,4-1' lyazole. 5. the solubilizer 1) an addition product of 1 to 60 moles of ethylene oxide with 1 mole of phenol further substituted with at least one 01-"11 alkyl group; and 11) ricinus oil 1 to 60 moles of ethylene oxide. 6. The liquid according to any one of claims 1 to 4, which is selected from the group consisting of: Addition product with 1 mole of Mataha ocderphenol;
and 11) an addition product of 1 to 60 moles of ethylene oxide with 1 mole of ricinus oil. 7. Claims 1 to 6, wherein the solvent is 2-butoxycetanol or butyl 2-hydroxyacetate
Liquids listed in any of the paragraphs. 81) 2-butoxyshetanol 10% to 80% by weight: 1i) 1-C2-(2,4-dichlorophenyl)
-X,3-dioxolan-2-ylmethyl]ii1)
A water-dilutable wood protection liquid containing an additional 100% by weight mixture of the addition product of nonylphenol with ethylene oxide, in which an average of 8 moles of ethylene oxide is reacted with 1 mole of nonylphenol. 9, i) Butyl 2-hydroxyacetate 10% to 80% by weight II) 1-C2-(2,4-dichlorophenyl)-
1,a-dioxolan-2-ylmethyl]-IB-1,
2,4-1 lyazole or its acid addition salt; and 1it) A water-dilutable wood protection liquid containing an additional 100% by weight mixture of the addition product of ethylene oxide of g cinnamon oil. 10. Claims 1 to 1 when used to protect wood
An aqueous mixture prepared by diluting a water-dilutable liquid according to any of clause 9.